Silicone compositions and their use in controlling the release or transfer of printed or molded patterns and transferring processes therefore

ABSTRACT

The present invention relates to silicone compositions that can be used to control the interface at which release occurs when a bi-layer or multi-layer structure comprising compositions as separate layers, and a pattern of a different material sandwiched in between, is separated. The present invention further relates to a process that utilizes these compositions to control the transfer or release of patterns deposited on a substrate.

The present invention relates to silicone compositions that can be usedto control the interface at which release occurs when a bi-layer ormulti-layer structure comprising compositions as separate layers, and apattern of a different material sandwiched in between, is separated. Thepresent invention further relates to a process that utilizes thesecompositions to control the transfer or release of patterns deposited ona substrate.

In many patterning processes controlled release at a specific interfaceis desired so that the type and location of the patterns produced in oron the substrate can be controlled. Examples of application include mostsoft lithography processes to fabricate microfluidic devices, where uponcuring, a polydimethylsiloxane has to release at a pre-determinedinterface so the shape, size, and location of the micro channels can becontrolled.

The Decal Transfer Microprinting method was disclosed by William RChilds and Ralph G. Nuzzo in an article entitled “Decal transfermicrolithography: A new soft-lithographic patterning method” in theJournal of the American Chemical Society, 124(45), pp. 13583-13596(2002). In that article, Childs and Nuzzo disclose apolydimethylsiloxane pattern formed on a backing layer, and the patternwas eventually transferred to a substrate permanently by engineeredadhesion and release. Such adhesion and release was achieved by heatand/or ultraviolet ozone treatment. The nature of ultraviolet ozonetreatment is such that environmental exposure conditions are importantvariables in this process. The essential feature of this process is thecontrolled release at a specific interface. It is desirable to have asystem that does not need heat or ultraviolet ozone treatment toengineer release at a specified interface.

Capillary micro contact printing used to pattern a conductive polymerpolyaniline was disclosed by Weng Sing Beh, In Tae Kim, Dong Qin, Younanxia, and George M. Whitesides in an article entitled “Formation ofpatterned microstructures of conducting polymers by soft lithography andapplications in microelectronic device fabrication”, Advanced Materials,11 (12), pp. 103 8-1041 (1999). This article discloses a relief patternformed on a polydimethylsiloxane surface by molding over a master andthe polydimethylsiloxane was placed on a substrate to form a channelnetwork. When a polyaniline emeraldine base in NMP was placed at theopen end of the channels the solution was drawn into the channels bycapillary force. Upon solvent evaporation, drying, and removal of thepolydimethylsiloxane mold, the polyaniline emeraldine was converted to aconductive polyaniline emeraldine salt by doping with HCl. In thisprocess the given nature of polydimethylsiloxane to release from thepolyaniline surface and the substrate surface makes fabricating thecircuit on the substrate possible. Processes such as this, however, donot have the freedom to easily switch between release at the interfaceof polydimethylsiloxane and polyaniline, and release at the interfacebetween the polyaniline and the substrate.

Deng et al. discloses a release process in an article entitled“Prototyping of masks, masters, and stamps/molds for soft lithographyusing an office printer and photographic reduction”, AnalyticalChemistry, 72(14), pp. 3176-3180 (2000). The process disclosed uses alow cost, office laser printer in combination with CAD software to printa pattern onto paper. Photo reduction of the pattern by imaging it ontoa 35 mm film or microfiche was used to obtain a master to moldpolydimethylsiloxane. The polydimethylsiloxane releases from the filmand from the developed image, replicating the patterns, and was used asstamps and molds for soft lithography processes.

Bottari in U.S. Pat. No. 6,280,552 discloses the use of controlledrelease of printed edge electrodes to a touch screen panel. In thisprocess the electrode was printed onto decal paper and covered with anover coat. The decal paper was removed and the electrode was transferredto the touch screen.

In all these processes, release occurs at one specific interfacepre-determined by the material composition. Some of the releasemechanisms have to be triggered by exposure to heat or ultravioletlight, some of them rely on the different surface properties ofdrastically different materials. The reverse of these processes, forexample, releasing from a polyaniline/substrate interface to provide anembedded conductive pathway in the molding polymers on top of thesubstrate, instead of releasing from a polydimethylsiloxane/polyanilineinterface to deposit it on the surface of the substrate, would requiredrastic change in materials, and thus change in other properties.

Consequently there is a need for better, more convenient, and reversiblecontrol of release or transfer of patterns placed between a substrateand a polymer molded on top of the substrate when the molded polymer andsubstrate are separated. It is desired that such control can be achievedwith minimum change of mechanical, optical, electrical, and otherproperties of the substrate and molding polymers.

This invention relates to silicone compositions and a process to controlthe transfer of a printed or molded pattern. When a pattern of a thirdmaterial is generated and placed in between such cured siliconecompositions, interfacial release will occur only on the interfacebetween the pattern and one composition of the pair when the pair isseparated. This allows a clean control of whether the surface feature ofa pattern will be replicated with high fidelity, or the pattern will becleanly transferred from the surface of one composition to the other.Those familiar with the electronics, microfluidics, and optic devicefabrication processes will appreciate the utility of such a process,enabled by the compositions, to build economically functional electricaland optical circuits, embedded three dimensional structures, two andthree dimensional channel networks, and so on. The compositions arepredominantly silicone based, and especially so when the variations ofother properties need to be minimized. But organic polymers can also beincluded in them.

Thus this invention relates to a silicone coating compositioncomprising:

-   (I) a first coating layer comprising a silicone composition (X)    obtained by a method comprising reacting:    -   (A) 100 parts by weight of at least one organosiloxane compound        containing an average of greater than two alkenyl groups per        molecule and having less than 1.5 mol % of silicon-bonded        hydroxy groups wherein the organosiloxane compound is selected        from        -   (i) an organosiloxane compound comprising R² ₃SiO_(1/2)            units and SiO_(4/2) units, wherein the molar ratio of R²            ₃SiO_(1/2) units to SiO_(4/2) units is from 0.05 to 4.0,        -   (ii) an organosiloxane compound comprising R² ₃SiO_(1/2)            units and R¹SiO_(3/2) units, wherein the molar ratio of R²            ₃SiO_(1/2) units to R¹SiO_(3/2) units is from 0.05 to 3.0,        -   (iii) an organosiloxane compound comprising R² ₃SiO_(1/2)            units, R¹SiO_(3/2) units, and SiO_(4/2) units, wherein the            molar ratio of R² ₃SiO_(1/2) units to R¹SiO_(3/2) units is            from 0.05 to 3.0, and the molar ratio of R² ₃SiO_(1/2) and            R¹SiO_(3/2) units combined to SiO_(4/2) units is from 4 to            99,        -   (iv) an organosiloxane compound comprising R² ₃SiO_(1/2)            units, R¹SiO_(3/2) units, and R² ₂SiO_(2/2) units, wherein            the molar ratio of R² ₃SiO_(1/2) units to R¹SiO_(3/2) units            and from 0.05 to 3.0, and the molar ratio of R² ₃SiO_(1/2)            units and R¹SiO_(3/2) units combined to R² ₂SiO_(2/2) units            is from 0.5 to 99,        -   (v) an organosiloxane compound comprising R² ₂SiO_(2/2)            units and R¹SiO_(3/2) units, wherein the molar ratio of R²            ₂SiO_(2/2) units to R¹SiO_(3/2) units is from 0.2 to 4.0,        -   (vi) an organosiloxane compound comprising R² ₂SiO_(2/2)            units and R² ₃SiO_(1/2) units, wherein the molar ratio of R²            ₂SiO_(2/2) units to R² ₃SiO_(1/2) units is from 0 to 15,000,            and        -   (vii) an organosiloxane compound comprising R² ₂SiO_(2/2)            units, R² ₃SiO_(1/2) units, and SiO_(2/2) units, wherein the            molar ratio of SiO_(2/2) units to R² ₂SiO_(2/2) units and R²            ₃SiO_(1/2) units combined is from 0.005 to 0.125            wherein R¹ is a hydrocarbon group free of aliphatic            unsaturation and R² is selected from R¹ and alkenyl groups;    -   (B) at least one organohydrogensilicon compound in an amount        sufficient to crosslink (A) selected from        -   (i) an organohydrogensilane compound having the formula HR³            ₂SiR⁴SiR³ ₂H wherein R³ is a hydrocarbon group free of            aliphatic unsaturation and R⁴ is a divalent hydrocarbon            group and        -   (ii) an organohydrogensiloxane compound having the formula            (HR³ _(a)SiO_((3-a)/2))_(b)(R¹ _(c)SiO_((4-c)/2))_(d)            wherein R¹ and R³ are as defined above, 1≦a≦2, 0≦c ≦3, the            value of b+d provides a molecular weight of 134 to 75,000,            and with the proviso that there are at least two SiH groups            per molecule;    -   (C) a catalytic amount of a hydrosilylation catalyst; and    -   optionally (D) an inorganic filler; and-   (II) a second coating layer in contact with the coating layer (I),    the second coating layer comprising a silicone composition (Y)    obtained by a method comprising reacting:

(A′) 100 parts by weight of at least one organosiloxane compoundcontaining an average of greater than two alkenyl groups per moleculeand having less than 1.5 mol % of silicon-bonded hydroxy groups, whereinthe organosiloxane compound is selected from

-   -   -   (i) an organosiloxane compound comprising R² ₂SiO_(2/2)            units and R² ₃SiO_(1/2) units, wherein the molar ratio of R²            ₂SiO_(2/2) units and R² ₃SiO_(1/2) units is from 0 to 15,000            and        -   (ii) an organosiloxane compound comprising R² ₃SiO_(1/2)            units and SiO_(4/2) units, wherein the molar ratio of R²            ₃SiO_(1/2) units to SiO_(4/2) units is from 0.05 to 4.0            wherein R² is selected from hydrocarbon groups free of            aliphatic unsaturation and alkenyl groups;

(B′) at least one organohydrogensilicon compound in an amount sufficientto crosslink (A′) selected from

-   -   -   (i) an organohydrogensilane compound having the formula            HR³ ₂SiR⁴SiR³ ₂H and        -   (ii) an organohydrogensiloxane compound having the formula            (HR³ _(a)SiO_((3-a)/2))_(b)(R¹ _(c)SiO_((4-c)/2))_(d)            wherein R¹ and R³ are each independently a hydrocarbon group            free of aliphatic unsaturation, R⁴ is a divalent hydrocarbon            group, 1≦a≦2, 0≦c≦3, the value of b+d provides a molecular            weight of 134 to 75,000, and with the proviso that there are            at least two SiH groups per molecule;

    -   (C′) a catalytic amount of a hydrosilylation catalyst; and

    -   optionally (D′) an inorganic filler        with the proviso that the molar ratio of R² ₂SiO_(2/2) units to        all other units combined is higher in composition (Y) than in        composition (X), and the surface energy of composition (Y) is        lower than composition (X). “Reacting” as used herein means        mixing components (A)-(C) and (A′)-(C′), respectively, and any        optional components at room temperature (20-25° C.) or heating a        mixture comprising components (A′)-(C′), and any optional        components to temperatures above room temperature such as at        temperatures of up to 200° C. Compositions (X) and (Y) may be        prepared by mixing (or mechanically agitating) components        (A)-(C) and (A′)-(C′), respectively, and any optional        components, to form a homogenous mixture. This may be        accomplished by any convenient mixing method known in the art        exemplified by a spatula, mechanical stirrers, in-line mixing        systems containing baffles and/or blades, powered in-line        mixers, homogenizers, a drum roller, a three-roll mill, a sigma        blade mixer, a bread dough mixer, and a two roll mill. The order        of mixing is not considered critical. Components (A)-(C) and        (A′)-(C′) and any optional components, may be pre-mixed and        applied or mixed during application if tack free time is short.

In compositions (X) and (Y) above, the hydrocarbon groups free ofaliphatic unsaturation are illustrated by alkyl groups such as methyl,ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, and arylgroups such as phenyl, naphthyl, benzyl, tolyl, xylyl, xenyl,methylphenyl, 2-phenylethyl, 2-phenyl-2-methylethyl, chlorophenyl,bromophenyl and fluorophenyl. The hydrocarbon group free of aliphaticunsaturation is typically methyl. The alkenyl groups in compositions (X)and (Y) above are illustrated by vinyl, allyl, butenyl, pentenyl,hexenyl, and decenyl. The alkenyl group is typically vinyl. The divalenthydrocarbon groups in compositions (X) and (Y) above are illustrated byalkylene groups selected from —(CH₂)_(x)—where x has a value of 2 to 10,—CH₂CH(CH₃)—, —CH₂CH(CH₃)CH₂—, and —CH₂CH₂CH(CH₂CH₃)CH₂CH₂CH₂—.

Component (A) is typically illustrated by an organosiloxane compoundcomprising ViMe₂SiO_(1/2) units and PhSiO_(3/2) units, where the molarratio of ViMe₂SiO_(1/2) units to PhSiO_(3/2) is from 0.05 to 3.0.Component (A) is illustrated by an organosiloxane having the formula(ViMe₂SiO_(1/2))₂₅(PhSiO_(3/2))₇₅.

Component (B) is typically illustrated by an organohydrogensilanecompound having the formula HMe₂Si-Ph-SiMe₂H.

Component (A′) is typically illustrated by an organosiloxane comprising(ViMe₂SiO_(1/2)) units, (Me₃SiO_(1/2)) units, (Me₂SiO_(2/2)) units, and(SiO₂) units wherein the ratio of (ViMe₂SiO_(1/2)) units+(Me₃SiO_(1/2))units to (Me₂SiO_(2/2)) units, is from 1/10000 to 1/5 and the ratio of(Me₂SiO_(2/2)) units to (SiO₂) units is from 200/1 to 1/4. Component(A′) is illustrated by an organosiloxane compound having the formula(ViMe₂SiO_(1/2))₂(Me₃SiO_(1/2))₁₅(Me₂SiO_(2/2))₈₁(SiO₂)₂₂.

Component (B′) is typically illustrated by an organohydrogensiloxanecompound having the formula Me₃SiO(Me₂SiO)_(x)(MeHSiO)_(y)SiMe₃ whereinthe value of x+y provides a molecular weight of 134 to 75,000 and thereare at least two SiH groups per molecule. Component (B′) is illustratedby an organosiloxane compound having the formulaMe₃SiO(Me₂SiO)₃(MeHSiO)₅SiMe₃.

Components (C) and (C′), the hydrosilylation catalysts are illustratedby any metal-containing catalyst which facilitates the reaction ofsilicon-bonded hydrogen atoms of components (B) and (B′), respectively,with the silicon-bonded alkenyl groups of components (A) and (A′),respectively. The metals are illustrated by ruthenium, rhodium,palladium, osmium, iridium, or platinum.

The metal-containing catalyst is typically a platinum-containingcatalyst since they are the most widely used and available and becausethey provide a more favorable effect for the compositions of thisinvention in terms of improved reaction rates. Platinum-containingcatalysts can be a compound or complex of a platinum metal.

One type of typical platinum-containing catalyst in the compositions ofthis invention is the composition that is obtained when chloroplatinicacid is reacted with an aliphatically unsaturated organosilicon compoundsuch as divinyltetramethyldisiloxane, because of its easy dispersibilityin organosilicon systems.

Preferably components (C) and (C′) are selected from chloroplatinicacid, alcohol modified chloroplatinic acids, olefin complexes ofchloroplatinic acid, complexes of chloroplatinic acid anddivinyltetramethyldisiloxane, fine platinum particles adsorbed on carboncarriers, platinum supported on metal oxide carriers such as Pt(Al₂O₃),platinum black, platinum acetylacetonate,platinum(divinyltetramethyldisiloxane), platinous halides exemplified byPtCl₂ and PtCl₄, Pt(CN)₂, complexes of platinous halides withunsaturated compounds exemplified by ethylene, propylene, andorganovinylsiloxanes, styrene hexamethyldiplatinum, and RhCl₃(Bu₂S)₃.

The amount of hydrosilylation catalyst that is used is not narrowlylimited as long as there is a sufficient amount to accelerate a reactionbetween Components (A) and (B), and between Components (A′) and (B′), atroom temperature or at temperatures above room temperature. The exactnecessary amount of this catalyst will depend on the particular catalystutilized and is not easily predictable. However, for platinum-containingcatalysts the amount can be as low as one weight part of platinum forevery one million weight parts of components (A)+(B) or components(A′)+(B′). The catalyst can be added at an amount 10 to 120 weight partsper one million parts of components (A)+(B) or (A′)+(B′), but istypically added in an amount from 10 to 60 weight parts per one millionparts of components (A)+(B) or, components (A′)+(B′).

Component (D) and (D′), the inorganic filler, is an optional componentwhich may be added to Compositions (X) and/or (Y). The inorganic filleris illustrated by hollow microsperes, fumed silica, precipitated silica,silicic anhydride, hydrous silicic acid, carbon black, ground quartz,calcium carbonate, magnesium carbonate, diatomaceous earth,wollastonite, calcined clay, clay, talc, kaolin, titanium oxide,bentonite, ferric oxide, zinc oxide, glass balloon, glass beads, mica,glass powder, glass balloons, coal dust, acrylic resin powder, phenolicresin powder, ceramic powder, zeolite, slate powder, organic fibers, andinorganic fibers. The amount of inorganic filler is typically in anamount from 5 to 30 per 100 parts of component (A).

This invention also relates to a method of making an article ofmanufacture comprising the steps of: (I) applying silicone composition(Y) to a substrate to form a coating 1 to 500 micrometer thick; (II)curing the silicone composition of step (I); (III) forming a pattern ontop of the product of step (II); (IV) applying silicone composition (X)over the pattern of step (III); (V) curing silicone composition (X) withthe proviso that the molar ratio of R² ₂SiO_(2/2) units to all otherunits combined is higher in silicone composition (Y) than in thesilicone composition (X), and the surface energy of the curedcomposition (Y) is lower than the cured silicone composition (X); and(VI) separating the cured silicone composition (X) of step (V) from thesubstrate.

Upon separation the pattern will be transferred and embedded into thecured composition (X). The separation between the two siliconecompositions, and between the silicone composition (Y) and the patternof step (III), is clean.

In the above method, compositions (X) and (Y) are as described above.Curing of the silicone compositions in the above method is typicallyaccomplished by exposing the composition to temperatures ranging from 25to 150° C., and more typically from 60 to 100° C. The method of applyingthe silicone composition is not critical to the present invention andcan be any of those known in the art for applying liquid coatings tosubstrates. The silicone composition in the above method can be appliedby such methods as dipping, spraying, wiping, brushing, extrusion, andcoextrusion. The substrate to which the silicone composition is appliedcan be any solid substrate such as glass, metal, or plastic.

When the surface profile of the pattern needs to be replicated andminimum or no transfer of the pattern into the molding layer is desired,the process can be reversed. In this case the silicone composition (X)is used as the coating, and the silicone composition (Y) will be themolding composition used on top of the coating. Thus this invention alsorelates to a method of making an article of manufacture comprising thesteps of:

-   (I) applying a silicone composition (X) to a substrate to form a    coating 1 to 500 micrometer thick wherein silicone composition (X)    is obtained by a method comprising reacting:

(A) 100 parts by weight of at least one organosiloxane compoundcontaining an average of greater than two alkenyl groups per moleculeand having less than 1.5 mol % of silicon-bonded hydroxy groups whereinthe organosiloxane compound is selected from

-   -   -   (i) an organosiloxane compound comprising R² ₃SiO_(1/2)            units and SiO_(4/2) units, wherein the molar ratio of R²            ₃SiO_(1/2) units to SiO_(4/2) units is from 0.05 to 4.0,        -   (ii) an organosiloxane compound comprising R² ₃SiO_(1/2)            units and R¹SiO_(3/2) units, wherein the molar ratio of R²            ₃SiO_(1/2) units to R¹SiO_(3/2) units is from 0.05 to 3.0,        -   (iii) an organosiloxane compound comprising R² ₃SiO_(1/2)            units, R¹SiO_(3/2) units, and SiO_(4/2) units, wherein the            molar ratio of R² ₃SiO_(1/2) units to R¹SiO_(3/2) units is            from 0.05 to 3.0, and the molar ratio of R² ₃SiO_(1/2) and            R¹SiO_(3/2) units combined to SiO_(4/2) units is from 4 to            99,        -   (iv) an organosiloxane compound comprising R² ₃SiO_(1/2)            units, R¹SiO_(3/2) units, and R² ₂SiO_(2/2) units, wherein            the molar ratio of R² ₃SiO_(1/2) units to R¹SiO_(3/2) units            is from 0.05 to 3.0, and the molar ratio of R² ₃SiO_(1/2)            units and R¹SiO_(3/2) units combined to R² ₂SiO_(2/2) units            is from 0.5 to 99,        -   (v) an organosiloxane compound comprising R² ₂SiO_(2/2)            units and R¹SiO_(3/2) units, wherein the molar ratio of R²            ₂SiO_(2/2) units to R¹SiO_(3/2) units is from 0.2 to 4.0,        -   (vi) an organosiloxane compound comprising R² ₂SiO_(2/2)            units and R² ₃SiO_(1/2) units, wherein the molar ratio of R²            ₂SiO_(2/2) units to R² ₃SiO_(1/2) units is from 0 to 15,000,            and        -   (vii) an organosiloxane compound comprising R² ₂SiO_(2/2)            units, R² ₃SiO_(1/2) units, and SiO_(2/2) units, wherein the            molar ratio of SiO_(2/2) units to R² ₂SiO_(2/2) units and R²            ₃SiO_(1/2) units combined is from 0.005 to 0.125            wherein R¹ is a hydrocarbon group free of aliphatic            unsaturation and R² is selected from R¹ and alkenyl groups;

    -   (B) at least one organohydrogensilicon compound in an amount        sufficient to crosslink (A) selected from        -   (i) an organohydrogensilane compound having the formula HR³            ₂SiR⁴SiR³ ₂H wherein R³ is a hydrocarbon group free of            aliphatic unsaturation and R⁴ is a divalent hydrocarbon            group and        -   (ii) an organohydrogensiloxane compound having the formula            (HR³ _(a)SiO_((3-a)/2))_(b)(R¹ _(c)SiO_((4-c)/2))_(d)            wherein R¹ and R³ are as defined above, 1≦a≦2, 0≦c≦3, the            value of b+d provides a molecular weight of 134 to 75,000,            and with the proviso that there are at least two SiH groups            per molecule;

    -   (C) a catalytic amount of a hydrosilylation catalyst; and

    -   optionally (D) an inorganic filler

-   (II) curing silicone composition (X);

-   (III) forming a pattern on top of the product of step (II);    (IV) applying a silicone composition (Y) over the pattern of    step (III) wherein silicone composition (Y) is obtained by a method    comprising reacting:    -   (A′) 100 parts by weight of at least one organosiloxane compound        containing an average of greater than two alkenyl groups per        molecule and having less than 1.5 mol % of silicon-bonded        hydroxy groups, wherein the organosiloxane compound is selected        from        -   (i) an organosiloxane compound comprising R² ₂SiO_(2/2)            units and R² ₃SiO_(1/2) units, wherein the molar ratio of R²            ₂SiO_(2/2) units and R² ₃SiO_(1/2) units is from 0 to 15,000            and        -   (ii) an organosiloxane compound comprising R² ₃SiO_(1/2)            units and SiO_(4/2) units, wherein the molar ratio of R²            ₃SiO_(1/2) units to SiO_(4/2) units is from 0.05 to 4.0            wherein R² is selected from hydrocarbon groups free of            aliphatic unsaturation and alkenyl groups;    -   (B′) at least one organohydrogensilicon compound in an amount        sufficient to crosslink (A′) selected from        -   (i) an organohydrogensilane compound having the formula            HR³ ₂SiR⁴SiR³ ₂H and        -   (ii) an organohydrogensiloxane compound having the formula            (HR³ _(a)SiO_((3-a)/2))_(b)(R¹ _(c)SiO_((4-c)/2))_(d)        -    wherein R¹ and R³ are each independently a hydrocarbon            group free of aliphatic unsaturation, R⁴ is a divalent            hydrocarbon group, 1≦a≦2, 0≦c≦3, the value of b+d provides a            molecular weight of 134 to 75,000, and with the proviso that            there are at least two SiH groups per molecule;    -   (C′) a catalytic amount of a hydrosilylation catalyst; and    -   optionally (D′) an inorganic filler;

-   (V) curing silicone composition (Y)

-   with the proviso that the molar ratio of R² ₂SiO_(2/2) units to all    other units combined is higher in silicone composition (X) than in    the silicone composition (Y), and the surface energy of the cured    composition (X) is lower than the cured silicone composition (Y);    and

-   (VI) separating the cured silicone composition (Y) of step (V) from    the substrate.

The ability to reverse the process derives from the minimizedcomposition differences between the two silicone compositions, and thewide range of mechanical properties attainable with these compositions.For most compositions, the only requirement for them to functionproperly is the higher R² ₂SiO_(2/2) units in one composition versus theother so that the surface energy of one of the cured compositions islower than the other.

The process can also be repeated as follows to build three-dimensionalembedded structures. Thus this invention also relates to a method ofmaking an article of manufacture comprising the steps of: (I) applyingsilicone composition (Y) to a substrate to form a coating 1 to 500micrometer thick; (II) curing the silicone composition of step (I);(III) forming a pattern on top of the product of step (II); (IV) placinga layer with pattern embedded in on top of the layer, in alignment withbut not in contact with the substrate; (V) applying silicone composition(X) onto the surface of the substrate or onto the surface of the layerthrough capillary flow; (VI) curing silicone composition (X); and (VII)separating the cured silicone composition (X) of step (VI) from thesubstrate. Silicone compositions (X) and (Y), the curing of the siliconecompositions, the method of applying the silicone compositions, and thesubstrate are all as defined above.

DRAWINGS

FIG. 1 is an optical microscope image of a carbon black ink patternprinted on the PET film coated with the mixture specified in Example 1.

FIG. 2 is an optical microscope image of the printed pattern, shown inFIG. 1, embedded into cured Silicone Composition B.

FIG. 3 is an SEM image of a carbon black ink pattern printed on the PETfilm, size of the dots approximately 5 μm in diameter.

FIG. 4 is an SEM image of the surface of the cured Silicone CompositionA after separation from the printed pattern, at the exact location as inFIG. 3.

FIG. 5 is an image of the embedded pattern into cured SiliconeComposition B.

FIG. 6 is an optical microscope image of the cross-section of theembedded pattern in cured Silicone Composition B.

FIG. 7 is an SEM image of the cross-section of the embedded pattern incured Silicone Composition B.

EXAMPLES

A VCA 2500 goniometer was used to measure water contact angle andsurface energies. Water and methylene iodide contact angles weremeasured by dropping three drops of each liquid on the samples andmeasuring the tangent angle to the coating. The averages and standarddeviations were obtained. The dispersive and polar surface energies werecalculated through a geometric mean model.

Example 1

A PET transparent film was coated by silicone composition (hereinafterdenoted Silicone Composition A) containing 24 parts by weight of anorganosiloxane compound comprising Me₃SiO_(1/2) units, ViMe₂SiO_(1/2)units, and SiO₂ units, where Vi denotes vinyl and Me denotes methyl, ina molar ratio of about 0.07 moles of Me₃SiO_(1/2) +ViMe₂SiO_(1/2) unitsper mole of SiO₂ units and where the organosiloxane compound containsfrom 1.75 to 2.3 weight percent of vinyl and 76 parts by weight of aliquid silicone rubber composition containing a mixture of 88 parts byweight of an organosiloxane compound comprising (ViMe₂SiO_(1/2))₂(Me₃SiO_(1/2))₁₅ (Me₂SiO_(2/2))₈₁ (SiO₂)₂₂ units and 6 parts by weightof an organohydrogensiloxane compound having the formulaMe₃SiO(Me₂SiO)₃(MeHSiO)₅SiMe₃. The coating was applied by hand operatedroll coater with a blade. The pressure applied on the blade controlledthe thickness of the coating and the pressure was adjusted so that a 2micrometer thick coating was obtained. The coating was cured at 125° C.for two hours and cooled to room temperature before use. This coatingaltered the surface energy of the PET film from 29.2 to 14.0 dyne/cm, asseen in Table 1.

A carbon black ink dot pattern was printed onto the coated PET film by alaser printer, as shown in FIG. 1, an optical microscope image of thepattern on the coated PET film. In the image the dots were approximately20 micrometers in diameter. Teflon bars one inch tall were glued ontofour sides around the printed pattern by a silicone sealant to form amold with the top open to the air. The mold was left at room temperatureand heated at 80° C. overnight to cure the silicone sealant.

A silicone composition (hereinafter denoted Silicone Composition B) wasprepared by mixing an organosiloxane compound comprising the units(PhSiO_(3/2))_(0.75) and (ViMe₂SiO_(1/2))_(0.25) with an organosiloxanecompound having the formula HMe₂Si-Ph-SiMe₂H so the SiH/SiVi ratio was1.1/1. To this mixture was then added a catalyst containing aplatinum-(1-ethynyl cyclohenxan-1-ol)-tetramethyl divinyl disiloxanecomplex dissolved in toluene at a platinum concentration of 1000 ppm.The catalyst was added at a weight ratio of 0.5 parts of catalyst per100 parts of the above mixture. The Silicone Composition B was thenpoured onto the top of the printed pattern encircled by Teflon bars, andleft at room temperature overnight to cure. The mold with SiliconeComposition B coated thereon was then heated at 60° C. for 2 hours tocomplete the cure. The cured silicone composition had a surface energyof 22 dynes/cm.

After cure, the mold was cooled to room temperature and the plaquecontaining cured Silicone Composition B as a top layer and SiliconeComposition A as a bottom layer was peeled off from the mold. As seen inFIG. 2, the printed pattern cleanly transferred to the silicone plaquefrom the surface of the coated PET film.

Example 2

Example 1 was repeated except that the coating thickness of CompositionA on the PET film was increased from 2 micrometers to approximately 20micrometers. As seen the surface energy was altered from 29.2 to 15.5dynes/cm, by this thicker coating. The same subsequent procedures asdescribed in Example 1 were followed and a clean transfer of the printedpattern was also observed.

Comparison Example 1

On an un-coated PET transparent film a carbon black ink dot pattern wasprinted by a laser printer, as shown in FIG. 3. A mold was made so thatthe pattern encircled by Teflon bars, similar to the mold used inExample 1, and the mold was cured similarly. Silicone Composition A waspoured onto the surface of the pattern in the mold. Silicone CompositionA was then cured at 60° C. for 2 hours. Silicone Composition A had asurface energy lower than the PET substrate. After cure the mold wascooled to room temperature and the cured Silicone Composition A waspeeled off from the mold. The surface topographic features of theprinted pattern were completely and cleanly replicated to the bottomsurface of the cured Silicone Composition A. No ink transfer wasobserved. FIG. 4 is an optical microscope image of the patternreplicated onto the cured Silicone Composition A surface at exactly thesame location as in FIG. 3.

Example 3

Procedures and compositions used were the same as in Example 1 exceptthe composition of the coating applied to the PET transparent film. Inthis example the coating composition was a mixture of 50 parts by weightof a mixture of 47.25 parts by weight of an organosiloxane compoundcomprising (ViMe₂SiO_(1/2))₄ (Me₃SiO_(1/2))₃₉ (SiO₂)₅₇ units and 3.72parts by weight of an organosiloxane compound comprising(ViMe₂SiO_(1/2))₂ (Me₂SiO_(2/2))₇₄₀ units and 50 parts by weight of anorganosiloxane compound comprising (ViMe₂SiO_(1/2))₂ (Me₂SiO_(2/2))₁₄₀units (hereinafter denoted Silicone Composition C). The cured coatingaltered the surface energy of the PET film from 29.2 to 15.1 dynes/cm.Clean transfer of printed carbon black ink patterns into curedComposition B was also observed with this coating on the PET film.

Example 4

Instead of using the 50/50 mixture described in Example 4 as thecoating, 100 parts by weight of the mixture of 47.25 parts by weight ofan organosiloxane compound comprising (ViMe₂SiO_(1/2))₄ (Me₃SiO_(1/2))₃₉(SiO₂)₅₇ units and 3.72 parts by weight of an organosiloxane compoundcomprising (ViMe₂SiO_(1/2))₂ (Me₂SiO_(2/2))₇₄₀ units (SiliconeComposition D) was used as the coating on the transparent PET film. Asseen in Table 1, the surface energy of the cured coating was 20.4dynes/cm, much higher than the mixture of Example 4. This coating wasnot suitable for the purpose of transferring or embedding the printedpattern into Silicone Composition B.

Example 5

Composition and procedures were the same as in Example 1. Instead of acarbon black ink dot pattern, carbon black ink patterns identical to aspecific design of RFID antenna were printed onto the coated PET film.These patterns were cleanly transferred into cured Silicone CompositionB, FIG. 5.

A close examination of the cross-section of the embedded pattern showedthat the pattern was transferred into the silicone composition bycontrolled release from the interface between the ink pattern and thecoated PET. In FIG. 6, an optical microscope image of the cross-sectionof the embedded pattern, the ink pattern was seen to reside on thesurface of Silicone Composition B. This was also confirmed by SEM.Silicone Composition B with the pattern was in turn embedded in an epoxyresin and cured. A cross-section was microtomed and observed under SEM.It again showed the location of the ink patterns was on the surface ofthe silicone composition as shown in FIG. 7. TABLE 1 Surface Energy ofthe PET Substrate With and Without Coatings Coating on Dispersive PolarTotal Example PET (dynes/cm) (dynes/cm) (dynes/cm) 1 Silicone 13.7 0.314.0 Composition A 2 Silicone 14.9 0.6 15.5 Composition A 3 Silicone12.6 2.5 15.1 Composition C 4 Silicone 20.2 0.2 20.4 Composition DComparison None 27.3 1.9 29.2 Example 1

1. A silicone coating composition comprising: (I) a first coating layercomprising a silicone composition (X) obtained by a method comprisingreacting: (A) 100 parts by weight of at least one organosiloxanecompound containing an average of greater than two alkenyl groups permolecule and having less than 1.5 mol % of silicon-bonded hydroxy groupswherein the organosiloxane compound is selected from (i) anorganosiloxane compound comprising R² ₃SiO_(1/2) units and SiO_(4/2)units, wherein the molar ratio of R² ₃SiO_(1/2) units to SiO_(4/2) unitsis from 0.05 to 4.0, (ii) an organosiloxane compound comprising R²₃SiO_(1/2) units and R¹SiO_(3/2) units, wherein the molar ratio of R²₃SiO_(1/2) units to R¹SiO_(3/2) units is from 0.05 to 3.0, (iii) anorganosiloxane compound comprising R² ₃SiO_(1/2) units, R¹SiO_(3/2)units, and SiO_(4/2) units, wherein the molar ratio of R² ₃SiO_(1/2)units to R¹SiO_(3/2) units is from 0.05 to 3.0, and the molar ratio ofR² ₃SiO_(1/2) and R¹SiO_(3/2) units combined to SiO_(4/2) units is from4 to 99, (iv) an organosiloxane compound comprising R² ₃SiO_(1/2) units,R¹SiO_(3/2) units, and R² ₂SiO_(2/2) units, wherein the molar ratio ofR² ₃SiO_(1/2) units to R¹SiO_(3/2) units is from 0.05 to 3.0, and themolar ratio of R² ₃SiO_(1/2) units and R¹SiO_(3/2) units combined to R²₂SiO_(2/2) units is from 0.5 to 99, (v) an organosiloxane compoundcomprising R² ₂SiO_(2/2) units and R¹SiO_(3/2) units, wherein the molarratio of R² ₂SiO_(2/2) units to R¹SiO_(3/2) units is from 0.2 to 4.0,(vi) an organosiloxane compound comprising R² ₂SiO_(2/2) units and R²₃SiO_(1/2) units, wherein the molar ratio of R² ₂SiO_(2/2) units to R²₃SiO_(1/2) units is from 0 to 15,000, and (vii) an organosiloxanecompound comprising R² ₂SiO_(2/2) units, R² ₃SiO_(1/2) units, andSiO_(2/2) units, wherein the molar ratio of SiO_(2/2) units to R²₂SiO_(2/2) units and R² ₃SiO_(1/2) units combined is from 0.005 to 0.125wherein R¹ is a hydrocarbon group free of aliphatic unsaturation and R²is selected from R¹ and alkenyl groups; (B) at least oneorganohydrogensilicon compound in an amount sufficient to crosslink (A)selected from (i) an organohydrogensilane compound having the formulaHR³ ₂SiR⁴SiR³ ₂H wherein R³ is a hydrocarbon group free of aliphaticunsaturation and R⁴ is a divalent hydrocarbon group and (ii) anorganohydrogensiloxane compound having the formula (HR³_(a)SiO_((3−a)/2))_(b)(R¹ _(c)SiO_((4−c)/2))_(d) wherein R¹ and R³ areas defined above, 1≦a≦2, 0≦c≦3, the value of b+d provides a molecularweight of 134 to 75,000, and with the proviso that there are at leasttwo SiH groups per molecule; (C) a catalytic amount of a hydrosilylationcatalyst; and optionally (D) an inorganic filler; and (II) a secondcoating layer in contact with the coating layer (I), the second coatinglayer comprising a silicone composition (Y) obtained by a methodcomprising reacting: (A′) 100 parts by weight of at least oneorganosiloxane compound containing an average of greater than twoalkenyl groups per molecule and having less than 1.5 mol % ofsilicon-bonded hydroxy groups, wherein the organosiloxane compound isselected from (i) an organosiloxane compound comprising R² ₂SiO_(2/2)units and R² ₃SiO_(1/2) units, wherein the molar ratio of R² ₂SiO_(2/2)units and R² ₃SiO_(1/2) units is from 0 to 15,000 and (ii) anorganosiloxane compound comprising R² ₃SiO_(1/2) units and SiO_(4/2)units, wherein the molar ratio of R² ₃SiO_(1/2) units to SiO4/₂ units isfrom 0.05 to 4.0 wherein R² is selected from hydrocarbon groups free ofaliphatic unsaturation and alkenyl groups; (B′) at least oneorganohydrogensilicon compound in an amount sufficient to crosslink (A′)selected from (i) an organohydrogensilane compound having the formulaHR³ ₂SiR⁴SiR³ ₂H and (ii) an organohydrogensiloxane compound having theformula(HR³ _(a)SiO_((3−a)/2))_(b)(R¹ _(c)SiO_((4−c)/2))_(d)  wherein R¹ and R³are each independently a hydrocarbon group free of aliphaticunsaturation, R⁴ is a divalent hydrocarbon group, 1≦a≦2, 0≦c≦3, thevalue of b+d provides a molecular weight of 134 to 75,000, and with theproviso that there are at least two SiH groups per molecule; (C′) acatalytic amount of a hydrosilylation catalyst; and optionally (D′) aninorganic filler with the proviso that the molar ratio of R² ₂SiO_(2/2)units to all other units combined is higher in composition (Y) than incomposition (X), and the surface energy of composition (Y) is lower thanComposition (X).
 2. A silicone coating composition according to claim 1,wherein the hydrocarbon group free of aliphatic unsaturation isindependently selected from methyl and phenyl and the alkenyl group isvinyl.
 3. A silicone coating composition according to claim 1, wherein:(A) is an organosiloxane compound comprising ViMe₂SiO_(1/2) units andPhSiO_(3/2) units, where the molar ratio of ViMc₂SiO_(1/2) units toPhSiO_(3/2) is from 0.05 to 3.0; (B) is an organohydrogensilane compoundhaving the formula HMe₂Si-Ph-SiMe₂H; (A′) is an organosiloxane compoundcomprising (ViMe₂SiO_(1/2)) units, (Me₃SiO_(1/2)) units, (Me₂SiO_(2/2))units, and (SiO₂) units wherein the ratio of (ViMe₂SiO_(1/2))units+(Me₃SiO_(1/2)) units to (Me₂SiO_(2/2)) units is from 1/10000 to1/5 and the ratio of (Me₂SiO_(2/2)) units to (SiO₂) units is from 200/1to 1/4; (B′) is an organohydrogensiloxane compound having the formulaMe3SiO(Me₂SiO)_(x)(MeHSiO)_(y)SiMe₃ wherein the value of x+y provides amolecular weight of 134 to 75,000 and there are at least two SiH groupsper molecule; (C) and (C′) are platinum-containing hydrosilylationcatalysts; and (D) and (D′) are selected from hollow microsperes, fumedsilica, precipitated silica, silicic anhydride, hydrous silicic acid,carbon black, ground quartz, calcium carbonate, magnesium carbonate,diatomaceous earth, wollastonite, calcined clay, clay, talc, kaolin,titanium oxide, bentonite, ferric oxide, zinc oxide, glass balloon,glass beads, mica, glass powder, glass balloons, coal dust, acrylicresin powder, phenolic resin powder, ceramic powder, zeolite, slatepowder, organic fibers, and inorganic fibers.
 4. A method of making anarticle of manufacture comprising the steps of: (I) applying a siliconecomposition (Y) to a substrate to form a coating 1 to 500 micrometerthick wherein silicone composition (Y) is obtained by a methodcomprising reacting: (A′) 100 parts by weight of at least oneorganosiloxane compound containing an average of greater than twoalkenyl groups per molecule and having less than 1.5 mol % ofsilicon-bonded hydroxy groups, wherein the organosiloxane compound isselected from (i) an organosiloxane compound comprising R² ₂SiO_(2/2)units and R² ₃SiO_(1/2) units, wherein the molar ratio of R² ₂SiO_(2/2)units and R² ₃SiO_(1/2) unit is between 0 and 15,000 and (ii) anorganosiloxane compound comprising R² ₃SiO_(1/2) units and SiO_(4/2)units, wherein the molar ratio of R² ₃SiO_(1/2) units to SiO_(4/2) unitsis from 0.05 to 4.0 wherein R² is selected from hydrocarbon groups freeof aliphatic unsaturation and alkenyl groups; (B′) at least oneorganohydrogensilicon compound in an amount sufficient to crosslink (A′)selected from (i) an organohydrogensilane compound having the formula(HR³ _(a)SiO_((3−a)/2))_(b)(R¹ _(c)SiO_((4−c)/2))_(d)  wherein R¹ and R³are each independently a hydrocarbon group free of aliphaticunsaturation, R⁴ is a divalent hydrocarbon group, 1≦a≦2, 0≦c≦3, thevalue of b+d provides a molecular weight of 134 to 75,000, and with theproviso that there are at least two SiH groups per molecule; (C′) acatalytic amount of a hydrosilylation catalyst; and optionally (D′) aninorganic filler (II) curing silicone composition (Y); (III) forming apattern on top of the product of step (II); (IV) applying a siliconecomposition (X) over the pattern of step (III) wherein siliconecomposition (X) is obtained by a method comprising reacting: (A) 100parts by weight of at least one organosiloxane compound containing anaverage of greater than two alkenyl groups per molecule and having lessthan 1.5 mol % of silicon-bonded hydroxy groups wherein theorganosiloxane compound is selected from (i) an organosiloxane compoundcomprising R² ₃SiO_(1/2) units and SiO_(4/2) units, wherein the molarratio of R² ₃SiO_(1/2) units to SiO_(4/2) units is from 0.05 to 4.0,(ii) an organosiloxane compound comprising R² ₃SiO_(1/2) units andR¹SiO_(3/2) units, wherein the molar ratio of R² ₃SiO_(1/2) units toR¹SiO_(3/2) units is from 0.05 to 3.0, (iii) an organosiloxane compoundcomprising R² ₃SiO_(1/2) units, R¹SiO_(3/2) units, and SiO_(4/2) units,wherein the molar ratio of R² ₃SiO_(1/2) units to R¹SiO_(3/2) units isfrom 0.05 to 3.0, and the molar ratio of R² ₃SiO_(1/2) and R¹SiO_(3/2)units combined to SiO_(4/2) units is from 4 to 99, (iv) anorganosiloxane compound comprising R² ₃SiO1/2 units, R¹SiO_(3/2) units,and R² ₂SiO_(2/2) units, wherein the molar ratio of R² ₃SiO_(1/2) unitsto R¹SiO_(3/2) units is from 0.05 to 3.0, and the molar ratio of R²₃SiO_(1/2) units and R¹SiO_(3/2) units combined to R² ₂SiO_(2/2) unitsis from 0.5 to 99, (v) an organosiloxane compound comprising R²₂SiO_(2/2) units and R¹SiO_(3/2) units, wherein the molar ratio of R²₂SiO_(2/2) units to R¹SiO_(3/2) units is from 0.2 to 4.0, (vi) anorganosiloxane compound comprising R² ₂SiO_(2/2) units and R² ₃SiO_(1/2)units, wherein the molar ratio of R² ₂SiO_(2/2) units to R² ₃SiO_(1/2)units is from 0 to 15,000, and (vii) an organosiloxane compoundcomprising R² ₂SiO_(2/2) units, R² ₃SiO_(1/2) units, and SiO_(2/2)units, wherein the molar ratio of SiO_(2/2) units to R² ₂SiO_(2/2) unitsand R² ₃SiO_(1/2) units combined is from 0.005 to 0.125 wherein R¹ is ahydrocarbon group free of aliphatic unsaturation and R² is selected fromR¹ and alkenyl groups; (B) at least one organohydrogensilicon compoundin an amount sufficient to crosslink (A) selected from (i) anorganohydrogensilane compound having the formulaHR³ ₂SiR⁴SiR³ ₂H  wherein R³ is a hydrocarbon group free of aliphaticunsaturation and R⁴ is a divalent hydrocarbon group and (ii) anorganohydrogensiloxane compound having the formula (HR³_(a)SiO_((3−a)/2))_(b)(R¹ _(c)SiO_((4−c)/2))_(d) wherein R¹ and R³ areas defined above, 1≦a≦2, 0≦c≦3, the value of b+d provides a molecularweight of 134 to 75,000, and with the proviso that there are at leasttwo SiH groups per molecule; (C) a catalytic amount of a hydrosilylationcatalyst; and optionally (D) an inorganic filler; (V) curing siliconecomposition (X) with the proviso that the molar ratio of R² ₂SiO_(2/2)units to all other units combined is higher in silicone composition (Y)than in the silicone composition (X), and the surface energy of thecured composition (Y) is lower than the cured silicone composition (X);and (VI) separating the cured silicone composition (X) of step (V) fromthe substrate.
 5. A method according to claim 4, wherein the hydrocarbongroup free of aliphatic unsaturation is independently selected frommethyl and phenyl and the alkenyl group is vinyl.
 6. A method accordingto claim 4, wherein: (A) is an organosiloxane compound comprisingViMe₂SiO_(1/2) units and PhSiO_(3/2) units, where the molar ratio ofViMe₂SiO_(1/2) units to PhSiO_(3/2) is from 0.05 to 3.0; (B) is anorganohydrogensilane compound having the formula HMe₂Si-Ph-SiMe₂H; (A′)is an organosiloxane compound comprising (ViMe₂SiO_(1/2)) units,(Me₃SiO_(1/2)) units, (Me₂SiO_(2/2)) units, and (SiO₂) units wherein theratio of (ViMe₂SiO_(1/2)) units+(Me₃SiO_(1/2)) units to (Me₂SiO_(2/2))units is from 1/10000 to 1/5 and the ratio of (Me₂SiO_(2/2)) units to(SiO₂) units is from 200/1 to 1/4; (B′) is an organohydrogensiloxanecompound having the formula Me₃SiO(Me₂SiO)_(x)(MeHSiO)_(y)SiMe₃ whereinthe value of x+y provides a molecular weight of 134 to 75,000 and thereare at least two SiH groups per molecule; (C) and (C′) areplatinum-containing hydrosilylation catalysts; and (D) and (D′) areselected from hollow microsperes, fumed silica, precipitated silica,silicic anhydride, hydrous silicic acid, carbon black, ground quartz,calcium carbonate, magnesium carbonate, diatomaceous earth,wollastonite, calcined clay, clay, talc, kaolin, titanium oxide,bentonite, ferric oxide, zinc oxide, glass balloon, glass beads, mica,glass powder, glass balloons, coal dust, acrylic resin powder, phenolicresin powder, ceramic powder, zeolite, slate powder, organic fibers, andinorganic fibers.
 7. A method of making an article of manufacturecomprising the steps of: (I) applying a silicone composition (X) to asubstrate to form a coating 1 to 500 micrometer thick wherein siliconecomposition (X) is obtained by a method comprising reacting: (A) 100parts by weight of at least one organosiloxane compound containing anaverage of greater than two alkenyl groups per molecule and having lessthan 1.5 mol % of silicon-bonded hydroxy groups wherein theorganosiloxane compound is selected from (i) an organosiloxane compoundcomprising R² ₃SiO_(1/2) units and SiO_(4/2) units, wherein the molarratio of R² ₃SiO_(1/2) units to SiO_(4/2) units is from 0.05 to 4.0,(ii) an organosiloxane compound comprising R² ₃SiO_(1/2) units andR¹SiO_(3/2) units, wherein the molar ratio of R² ₃SiO_(1/2) units toR¹SiO_(3/2) units is from 0.05 to 3.0, (iii) an organosiloxane compoundcomprising R² ₃SiO_(1/2) units, R¹SiO_(3/2) units, and SiO_(4/2) units,wherein the molar ratio of R² ₃SiO_(1/2) units to R¹SiO_(3/2) units isfrom 0.05 to 3.0, and the molar ratio of R² ₃SiO_(1/2) and R¹SiO_(3/2)units combined to SiO_(4/2) units is from 4 to 99, (iv) anorganosiloxane compound comprising R² ₃SiO_(1/2) units, R¹SiO_(3/2)units, and R² ₂SiO_(2/2) units, wherein the molar ratio of R² ₃SiO_(1/2)units to R¹SiO_(3/2) units is from 0.05 to 3.0, and the molar ratio ofR² ₃SiO_(1/2) units and R¹SiO_(3/2) units combined to R² ₂SiO_(2/2)units is from 0.5 to 99, (v) an organosiloxane compound comprising R²₂SiO_(2/2) units and R¹SiO_(3/2) units, wherein the molar ratio of R²₂SiO_(2/2) units to R¹SiO_(3/2) units is from 0.2 to 4.0, and (vi) anorganosiloxane compound comprising R² ₂SiO_(2/2) units and R² ₃SiO_(1/2)units, wherein the molar ratio of R² ₂SiO_(2/2) units to R² ₃SiO_(1/2)units is from 0 to 15,000 wherein R¹ is a hydrocarbon group free ofaliphatic unsaturation and R² is selected from R¹ and alkenyl groups;(B) at least one organohydrogensilicon compound in an amount sufficientto crosslink (A) selected from (i) an organohydrogensilane compoundhaving the formula HR³ ₂SiR⁴SiR³ ₂H wherein R³ is a hydrocarbon groupfree of aliphatic unsaturation and R⁴ is a divalent hydrocarbon groupand (ii) an organohydrogensiloxane compound having the formula (HR³_(a)SiO_((3−a)/2)) _(b)(R¹ _(c)SiO_((4−c)/2)d) wherein R1 and R3 are asdefined above, 1≦a≦2, 0≦c≦3, the value of b+d provides a molecularweight of 134 to 75,000, and with the proviso that there are at leasttwo SiH groups per molecule; (C) a catalytic amount of a hydrosilylationcatalyst; and optionally (D) an inorganic filler (II) curing siliconecomposition (X); (III) forming a pattern on top of the product of step(II); (IV) applying a silicone composition (Y) over the pattern of step(III) wherein silicone composition (Y) is obtained by a methodcomprising reacting: (A′) 100 parts by weight of at least oneorganosiloxane compound containing an average of greater than twoalkenyl groups per molecule and having less than 1.5 mol % ofsilicon-bonded hydroxy groups, wherein the organosiloxane compound isselected from (i) an organosiloxane compound comprising R² ₂SiO_(2/2)units and R² ₃SiO_(1/2) units, wherein the molar ratio of R² ₂SiO_(2/2)units and R² ₃SiO_(1/2) units is from 0 to 15,000 and (ii) anorganosiloxane compound comprising R² ₃SiO_(1/2) units and SiO_(4/2)units, wherein the molar ratio of R² ₃SiO_(1/2) units to SiO_(4/2) unitsis from 0.05 to 4.0 wherein R² is selected from hydrocarbon groups freeof aliphatic unsaturation and alkenyl groups; (B′) at least oneorganohydrogensilicon compound in an amount sufficient to crosslink (A′)selected from (i) an organohydrogensilane compound having the formulaHR³ ₂SiR⁴SiR³ ₂H and (ii) an organohydrogensiloxane compound having theformula(HR³ _(a)SiO_((3−a)/2))_(b)(R¹ _(c)SiO_((4−c)/2))_(d)  wherein R¹ and R³are each independently a hydrocarbon group free of aliphaticunsaturation, R⁴ is a divalent hydrocarbon group, 1≦a≦2, 0≦c≦3, thevalue of b+d provides a molecular weight of 134 to 75,000, and with theproviso that there are at least two SiH groups per molecule; (C′) acatalytic amount of a hydrosilylation catalyst; and optionally (D′) aninorganic filler; (V) curing silicone composition (Y) with the provisothat the molar ratio of R² ₂SiO_(2/2) units to all other units combinedis higher in silicone composition (X) than in the silicone composition(Y), and the surface energy of the cured composition (X) is lower thanthe cured silicone composition (Y); and (VI) separating the curedsilicone composition (Y) of step (V) from the substrate.
 8. A methodaccording to claim 7, wherein the hydrocarbon group free of aliphaticunsaturation is independently selected from methyl and phenyl and thealkenyl group is vinyl.
 9. A method according to claim 7, wherein: (A)is an organosiloxane compound comprising ViMe₂SiO_(1/2) units andPhSiO_(3/2) units, where the molar ratio of ViMe₂SiO_(1/2) units toPhSiO_(3/2) is from 0.05 to 3.0; (B) is an organohydrogensilane compoundhaving the formula HMe₂Si-Ph-SiMe₂H; (A′) is an organosiloxane compoundcomprising (ViMe₂SiO_(1/2)) units, (Me₃SiO_(1/2)) units, (Me₂SiO_(2/2))units, and (SiO₂) units wherein the ratio of (ViMe₂SiO_(1/2))units+(Me₃SiO_(1/2)) units, to (Me₂SiO_(2/2)) units, is from 1/10000 to1/5 and the ratio of (Me₂SiO_(2/2)) units to (SiO₂) units is from 200/1to 1/4; (B′) is an organohydrogensiloxane compound having the formulaMe₃SiO(Me₂SiO)_(x)(MeHSiO)_(y)SiMe₃ wherein the value of x+y provides amolecular weight of 134 to 75,000 and there are at least two SiH groupsper molecule; (C) and (C′) are platinum-containing hydrosilylationcatalysts; and (D) and (D′) are selected from hollow microsperes, fumedsilica, precipitated silica, silicic anhydride, hydrous silicic acid,carbon black, ground quartz, calcium carbonate, magnesium carbonate,diatomaceous earth, wollastonite, calcined clay, clay, talc, kaolin,titanium oxide, bentonite, ferric oxide, zinc oxide, glass balloon,glass beads, mica, glass powder, glass balloons, coal dust, acrylicresin powder, phenolic resin powder, ceramic powder, zeolite, slatepowder, organic fibers, and inorganic fibers.
 10. A method of making anarticle of manufacture comprising the steps of: (I) applying a siliconecomposition (Y) to a substrate to form a coating 1 to 500 micrometerthick wherein silicone composition (Y) is obtained by a methodcomprising reacting: (A′) 100 parts by weight of at least oneorganosiloxane compound containing an average of greater than twoalkenyl groups per molecule and having less than 1.5 mol % ofsilicon-bonded hydroxy groups, wherein the organosiloxane compound isselected from (i) an organosiloxane compound comprising R² ₂SiO_(2/2)units and R² ₃SiO_(1/2) units, wherein the molar ratio of R² ₂SiO_(2/2)units and R² ₃SiO_(1/2) units is from 0 to 15,000 and (ii) anorganosiloxane compound comprising R² ₃SiO_(1/2) units and SiO_(4/2)units, wherein the molar ratio of R² ₃SiO_(1/2) units to SiO_(4/2) unitsis from 0.05 to 4.0 wherein R² is selected from hydrocarbon groups freeof aliphatic unsaturation and alkenyl groups; (B′) at least oneorganohydrogensilicon compound in an amount sufficient to crosslink (A′)selected from (i) an organohydrogensilane compound having the formulaHR³ ₂SiR⁴SiR³ ₂H and (ii) an organohydrogensiloxane compound having theformula(HR³ _(a)SiO_((3−a)/2))_(b)(R¹ _(c)SiO_((4−c)/2))_(d)  wherein R¹ and R³are each independently a hydrocarbon group free of aliphaticunsaturation, R⁴ is a divalent hydrocarbon group, 1≦a≦2, 0≦c≦3, thevalue of b+d provides a molecular weight of 134 to 75,000, and with theproviso that there are at least two SiH groups per molecule; (C′) acatalytic amount of a hydrosilylation catalyst; and optionally (D′) aninorganic filler; (II) curing silicone composition (Y); (III) forming apattern on top of the product of step (II); (IV) placing a layer withthe pattern embedded in on top of the layer, in alignment with but notin contact with the substrate; (V) applying a silicone composition (X)onto the surface of the substrate or onto the surface of the layerthrough capillary flow wherein silicone composition (X) is obtained by amethod comprising reacting: (A) 100 parts by weight of at least oneorganosiloxane compound containing an average of greater than twoalkenyl groups per molecule and having less than 1.5 mol % ofsilicon-bonded hydroxy groups wherein the organosiloxane compound isselected from (i) an organosiloxane compound comprising R² ₃SiO_(1/2)units and SiO_(4/2) units, wherein the molar ratio of R² ₃SiO _(1/2)units to SiO_(4/2) units is from 0.05 to 4.0, (ii) an organosiloxanecompound comprising R² ₃SiO_(1/2) units and R¹SiO_(3/2) units, whereinthe molar ratio of R² ₃SiO_(1/2) units to R¹SiO_(3/2) units is from 0.05to 3.0, (iii) an organosiloxane compound comprising R² ₃SiO_(1/2) units,R¹SiO_(3/2) units, and SiO_(4/2) units, wherein the molar ratio of R²₃SiO_(1/2) units to R¹SiO_(3/2) units is from 0.05 to 3.0, and the molarratio of R² ₃SiO_(1/2) and R¹SiO_(3/2) units combined to SiO_(4/2) unitsis from 4 to 99, (iv) an organosiloxane compound comprising R²₃SiO_(1/2) units, R¹SiO_(3/2) units, and R² ₂SiO_(2/2) units, whereinthe molar ratio of R² ₃SiO_(1/2) units to R¹SiO_(3/2) units is from 0.05to 3.0, and the molar ratio of R² ₃SiO_(1/2) units and R¹SiO_(3/2) unitscombined to R² ₂SiO_(2/2) units is from 0.5 to 99, (v) an organosiloxanecompound comprising R² ₂SiO_(2/2) units and R¹SiO_(3/2) units, whereinthe molar ratio of R² ₂SiO_(2/2) units to R¹SiO_(3/2) units is from 0.2to 4.0, and (vi) an organosiloxane compound comprising R² ₂SiO_(2/2)units and R² ₃SiO_(1/2) units, wherein the molar ratio of R² ₂SiO_(2/2)units to R² ₃SiO_(1/2) units is from 0 to 15,000 wherein R¹ is ahydrocarbon group free of aliphatic unsaturation and R² is selected fromR¹ and alkenyl groups; (B) at least one organohydrogensilicon compoundin an amount sufficient to crosslink (A) selected from (i) anorganohydrogensilane compound having the formula HR³ ₂SiR⁴SiR³ ₂Hwherein R³ is a hydrocarbon group free of aliphatic unsaturation and R⁴is a divalent hydrocarbon group and (ii) an organohydrogensiloxanecompound having the formula (HR³ _(a)SiO_((3−a)/2))_(b)(R¹_(c)SiO_((4−c)/2))_(d) wherein R¹ and R³ are as defined above, 1≦a≦2,0≦c≦3, the value of b+d provides a molecular weight of 134 to 75,000,and with the proviso that there are at least two SiH groups permolecule; (C) a catalytic amount of a hydrosilylation catalyst; andoptionally (D) an inorganic filler; (VI) curing silicone composition (X)with the proviso that the molar ratio of R² ₂SiO_(2/2) units to allother units combined is higher in silicone composition (Y) than in thesilicone composition (X), and the surface energy of the curedcomposition (Y) is lower than the cured silicone composition (X); and(VII) separating the cured silicone composition (X) of step (VI) fromthe substrate.